High performance photocurable optically clear adhesive

ABSTRACT

The present invention is an optically clear, curable adhesive including a polyvinylbutyral, a polyurethane (meth)acrylate, a (meth)acrylate monomer, and a photoinitiator. The polyvinylbutyral has a dynamic viscosity of between about 9 and about 13 mPA·s and a polyvinyl alcohol weight percent of less than about 18%. The polyurethane (meth)acrylate includes the reaction product of a diol, at least one diisocyanate, and a hydroxyfunctional (meth)acrylate or an isocyanatofunctional (meth)acrylate. When the optically clear, curable adhesive is placed between two transparent substrates and made into a laminate, the laminate has a haze of less than about 6%, a transmission of greater than about 88%, and an optical clarity of greater than about 98% when cured. The optically clear, curable adhesive also has a peel adhesion of at least about 100 g/cm based on ASTM 3330 when cured.

FIELD OF THE INVENTION

The present invention is generally related to optically clear adhesives.In particular, the present invention is a photocurable optically clearadhesive.

BACKGROUND

Compared to traditional optically clear adhesive (OCA) films, it isbelieved that photocurable optically clear adhesives (PCOCAs) canprovide thinner gaps, better control over thickness, less to no stressfrom lamination, and better conformability to the various features of adisplay assembly, such as ink steps. Therefore, liquid optically clearadhesives (LOCAs) are becoming more prevalent in the display industry tofill the air gap between a cover glass and indium-tin oxide (ITO) touchsensors, between ITO touch sensors and liquid crystal modules, ordirectly between the cover glass and the liquid crystal module.

The display industry is currently moving toward liquid crystal module(LCM) bonding in which it is believed that a low shrinkage, low modulusmaterial is necessary for optical performance and LCM bonding.Furthermore, it is also critical to ensure that the OCA does not have adeleterious effect on the LCM's appearance (e.g. mura effect, opticaldefects, etc.), has high adhesion, and is optically reliable underenvironmental conditions, such as exposure to a temperature of 85° C. orconditions of 65° C./90% RH for an extended period of time.

Current LOCA products are predominantly prepared from acrylic monomersor reactive oligomers based on acrylic monomers. However, these productseither have significant shrinkage that may be detrimental for LCMbonding or require further optimizations. Polyacrylate based oligomerswith curable functionality are also used in LOCA materials to achievehigh adhesion, low shrinkage and low modulus LCM bonding. However, theseoligomers often require a relatively high concentration of polarmonomers, such as 4-hydroxybutyl acrylate, in order to achieve coatableviscosity and optical reliability under environmental aging conditions,which typically require more than 800 hours of optical stability at 85°C. and 65° C./90% RH. Using high levels of diluent monomers can directlycontribute to the shrinkage of the adhesive upon cure and can offset thebenefit of using polyacrylate oligomers.

SUMMARY

In one embodiment, the present invention is an optically clear, curableadhesive including a polyvinylbutyral, a polyurethane (meth)acrylate, a(meth)acrylate monomer, and a photoinitiator. The polyvinylbutyral has adynamic viscosity of between about 9 and about 13 mPA·s and a polyvinylalcohol weight percent of less than about 18%. The polyurethane(meth)acrylate includes the reaction product of a diol, at least onediisocyanate, and a hydroxyfunctional (meth)acrylate or anisocyanatofunctional (meth)acrylate. When the optically clear, curableadhesive is placed between two transparent substrates and made into alaminate, the laminate has a haze of less than about 6%, a transmissionof greater than about 88%, and an optical clarity of greater than about98% when cured. The optically clear, curable adhesive also has a peeladhesion of at least about 100 g/cm based on ASTM 3330 when cured.

In another embodiment, the present invention is an optically clearlaminate including a first substrate, a second substrate, and anoptically clear, curable adhesive positioned between the first substrateand the second substrate. The optically clear, curable adhesive includesa polyvinylbutyral, a polyurethane (meth)acrylate, a (meth)acrylatemonomer, and a photoinitiator. The polyvinylbutyral has a dynamicviscosity of between about 9 and about 13 mPA·s and a polyvinyl alcoholweight percent of less than about 18%. The polyurethane (meth)acrylateincludes the reaction product of a diol, at least one diisocyanate, anda hydroxyfunctional (meth)acrylate or an isocyanatofunctional(meth)acrylate. When the optically clear, curable adhesive is placedbetween two transparent substrates and made into a laminate, thelaminate has a haze of less than about 6%, a transmission of greaterthan about 88% and an optical clarity of greater than about 98% whencured. The optically clear, curable adhesive also has a peel adhesion ofat least about 100 g/cm based on ASTM 3330.

DETAILED DESCRIPTION

The present invention is a high performance, photocurable opticallyclear adhesive (PCOCA) construction. The PCOCA is a curable, opticallyclear adhesive with superior optical clarity as well as superioradhesion and may be used, for example, in a display assembly for bondinga substrate to glass. The PCOCA materials are prepared from blends ofcurable (meth)acrylic and polyurethane (or polyurea) based reactiveoligomers.

The PCOCA of the present invention includes a polyvinylbutyral, apolyurethane acrylate, a (meth)acrylate monomer, and a photoinitiator.In one embodiment, the PCOCA includes between about 30% and about 70%,particularly between about 40% and about 60%, and more particularlybetween about 40% and about 55% by weight polyvinylbutyral (excludingphotoinitiator); between about 10% and about 60%, particularly betweenabout 15% and about 40%, and more particularly between about 20% andabout 30% by weight polyurethane (meth)acrylate (excludingphotoinitiator); and between about 10% and about 60%, particularlybetween about 15% and about 40%, and more particularly between about 20%and about 30% by weight (meth)acrylate monomer (excludingphotoinitiator). In an embodiment, the weight percentages of thepolyvinylbutyral, polyurethane (meth)acrylate, and (meth)acrylatemonomer in the formulation (excluding photoinitiator) total 100%. Inanother embodiment, the weight percentages of the polyvinylbutyral,polyurethane (meth)acrylate, and (meth)acrylate monomer in theformulation (excluding photoinitiator) total less than 100% due to thepresence of additives in the formulation.

In one embodiment, the polyvinylbutyral has a dynamic viscosity ofbetween about 9 and about 30 mPA·s (as measured according to DIN 53015,10% solids in solution, in ethanol containing 5% water) with a polyvinylalcohol weight percent of less than about 21%. In particular, thepolyvinylbutyral has a polyvinyl alcohol weight percent of between about14% and about 21% and a polyvinyl acetate weight percent of betweenabout 1% and about 8%. In one embodiment, the polyvinylbutyral has aweight average molecular weight (Mw) of between about 10,000 g/mol andabout 25,000 g/mol. Examples of suitable commercially availablepolyvinylbutyrals include, but are not limited to, Mowital B14S, MowitalB16H, and Mowital 20H, all available from Kuraray America, Inc. locatedin Houston, Tex.

Polyurethane (meth)acrylates are polyurethane polymers having one ormore (meth)acrylate groups attached to the polyurethane polymer.Polyurethanes are polymers that are useful in many applications, such asadhesives. Polyurethanes may be prepared from starting materials thatinclude isocyanato functional group-containing compounds, such aspolyisocyanates (preferably diisocyanates) and compounds having afunctional group reactive with the isocyanate groups, such as polyolsand/or polyamines (preferably diols and/or diamines). In someembodiments, polyurethanes are alternating, block, star block, orsegmented copolymers (or combinations thereof). Polyurethanes may alsocontain other chemical moieties, such as alkyl, aryl, acrylate, ether,ester, and carbonate groups, and mixtures thereof. In one embodiment,the polyurethane (meth)acrylate has a weight average molecular weight(Mw) of between about 2,745 g/mol and about 63,000 g/mol.

Polyurethane (meth)acrylates may have (meth)acrylate functionality atone or more chain ends and at other sites in the polymer chain. As anonlimiting example, a (meth)acrylate diol (e.g., 2-glyceryl(meth)acrylate) may be used to make a polyurethane (meth)acylate havingacrylate groups that are at sites not near the polymer chain ends. In aone embodiment, the polyurethane (meth)acrylate has (meth)acrylatefunctionality at the chain ends.

Polyurethane (meth)acrylates may contain other functionality (e.g.,ether, ester, and/or carbonate functional groups) by selection of thestarting materials used to make them. As a nonlimiting example,poly(tetramethylene oxide) may be used to make a polyurethane(meth)acrylate that also comprises ether functional groups. Aparticularly suitable polyurethane (meth)acrylate comprises urethane,(meth)acrylate, and ether functional groups. Another particularlysuitable polyurethane (meth)acrylate comprises urethane, (meth)acrylate,and ester functional groups.

Examples of commercially available suitable polyurethane (meth)acrylatesinclude, but are not limited to: CN978, CN981, and CN991 available fromSartomer Americas located in Exton, Pa. In one embodiment, thepolyurethane (meth)acrylate has a polydispersity of between about 1.3and about 3.0. The polydispersity index is used as a measure of thebroadness of a molecular weight distribution of a polymer, and isdefined by the ratio of the number average molecular weight:weightaverage molecular weight. The larger the polydispersity index, thebroader the molecular weight distribution of the polymer.

The polyurethane (meth)acrylate of the present invention includes apolyurethane (meth)acrylate comprising the reaction product of a diol,at least one diisocyanate, and a hydroxyfunctional (meth)acrylate or anisocyanatofunctional (meth)acrylate. A (meth)acrylate is defined to bean ester of acrylic or methacrylic acid. The diol(s) and diisocyanate(s)may be present in different ratios, depending at least in part on themolecular weights of the diol(s) and diisocyanate(s) and the desiredmolecular weight of the resulting polyurethane (meth)acrylate. As iswell-known in the art of polyurethane formulation, diols may be selectedto provide flexibility and conformability to polyurethane(meth)acrylates and to adhesives comprising polyurethane(meth)acrylates. Diols may also be selected to provide compatibility ofpolyurethane (meth)acrylates with polyvinylbutyral or other componentsof an adhesive formulation. Without being bound by theory, compatibilitybetween the polyvinylbutyral and the polyurethane (meth)acrylatematerials is thought to be necessary to obtain the desired opticalproperties in the resulting adhesives.

Diols may also be selected for their ability to contribute propertiesdesired in the resulting adhesive, such as adhesive properties andoptical properties. In one embodiment, diols based onpoly(tetramethylene oxide) and on polycaprolactone are suitable in thepolyurethane (meth)acrylates used in the adhesive formulations of theinvention, and diols based on poly(tetramethylene oxide) areparticularly suitable in polyurethane (meth)acrylates used in theadhesive formulations of the invention. In one embodiment, the diol mayinclude lower molecular weight diols such as ethylene glycol, orbutanediol. In one embodiment, the diol is selected from one of apoly(tetramethylene oxide) diol having a number average molecular weight(M_(n)) of about 2000 g/mol or less, a poly(propylene oxide) diol havinga number average molecular weight of about 2000 g/mol or less, and apolycaprolactone diol having a number average molecular weight of about2000 g/mol or less. An example of a suitable commercially availablepoly(tetramethylene oxide) diol having a number average molecular weightof about 1000 g/mol includes, but is not limited to, PolyTHF 1000Polyether, available from BASF Corp. located in Florham Park, N.J.

Diisocyanates may also be selected for their ability to provideproperties desired in the polyurethane (meth)acrylate and in theresulting adhesives, such as adhesive properties and optical properties.In one embodiment, the isocyanates include aliphatic isocyanates.Particularly suitable isocyanates include aliphatic diisocyanates. As isknown in the art, an aliphatic isocyanate is one in which each of theone or more isocyanato group(s) is attached by a chemical bond to analiphatic carbon atom. However, it is acceptable that an aliphaticisocyanate molecule may also contain an aromatic moiety that is notattached to any of the one or more isocyanato groups. By thisdefinition, methylene diphenyl diisocyanate (MDI) and toluenediisocyanate (TDI) are not aliphatic isocyanates, but are considered tobe aromatic isocyanates. However, meta-tetramethylxylylene diisocyanateand para-tetramethylxylylene diisocyanate (m-TMXDI and p-TMXDI,respectively) are considered aliphatic isocyanates even though theycontain an aromatic ring (see structures below). Of course, isocyanatescontaining no aromatic moiety in their molecular structure, such asisophorone diisocyanate (IPDI), are aliphatic isocyanates.

Examples of suitable diisocyanates include, but are not limited to:2,6-toluene diisocyanate (TDI),methylenedicyclohexylene-4,4′-diisocyanate (H12MDI),3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI),1,6-diisocyanatohexane (HDI), tetramethyl-m-xylylene diisocyanate, amixture of 2,2,4- and 2,4,4-Trimethyl-1,6-diisocyanatohexane (TMXDI),trans-1,4-hydrogenated xylylene diisocyanates (H6XDI) and combinationsthereof. In one embodiment, the diisocyanate is an aliphaticdiisocyanate.

The polyurethane (meth)acrylate of the present invention may alsoinclude a hydroxyfunctional (meth)acrylate or an isocyanatofunctional(meth)acrylate. Monofunctional molecules may also be used in thepreparation of polyurethanes. For example, monofunctional molecules suchas monofunctional alcohol- and isocyanate-containing molecules can beused to introduce functional groups at or near the polyurethane chainends during polymer synthesis. Suitable monofunctional alcohols include2-hydroxyethyl acrylate (HEA) and 2-hydroxyethyl methacrylate (HEMA).Another monofunctional alcohol providing more than one acrylate peralcohol group is exemplified by glycerol dimethacrylate, also known asbis(methacryloyloxy)propanol (mixture of 1,2- and 1,3-form), Suitablemonofunctional isocyanates include 2-isocyanatoethyl acrylate and2-isocyanatoethyl methacrylate. Another monofunctional isocyanateproviding more than one acrylate per isocyanate group is exemplified by.1,1-bis(acryloyloxymethyl)ethyl isocyanate, available from CBC America,Commack, N.Y. All of these compounds may be used to synthesizepolyurethanes with (meth)acrylate end groups.

Suitable polyurethane (meth)acrylates are prepared by combining amonofunctional alcohol and a difunctional alcohol with a diisocyanate.In one embodiment, the monofunctional alcohol is selected from HEA,HEMA, and combinations thereof. Other suitable polyurethanes areprepared by combining a monofunctional isocyanate and a difunctionalisocyanate with a diol. In one embodiment, the monofunctional isocyanateis selected from 2-isocyanatoethyl acrylate, 2-isocyanatoethylmethacrylate. In another embodiment, polyurethane (meth)acrylates areprepared by combining a monofunctional alcohol, as discussed above, witha diisocyanate. Another example of a monofunctional alcohol suitable forreaction with a diisocyanate is caprolactone extended hydroxyethyl(meth)acrylate. An example of a commercially suitable caprolactoneextended hydroxyethyl (meth)acrylate includes, but is not limited to,SR495, available from Sartomer Americas located in Exton, Pa.

A variety of methods may be used to synthesize polyurethane(meth)acrylates. The starting materials may be combined by methods knownin the art and in selected ratios to produce polyurethane(meth)acrylates with desired properties, such as a selected molecularweight. One method known in the art is to combine a polyfunctionalalcohol (preferably a diol) with a polyisocyanate (preferably adiisocyanate) to produce a polyurethane prepolymer. A polyurethaneprepolymer may have either alcohol or isocyanate functional groups onthe molecular chain ends, depending on the selected ratio of polyalcoholto polyisocyanate.

In an embodiment in which a polyurethane prepolymer is synthesized byreaction of a diol and a diisocyanate, the ratio of diisocyanate to diolis chosen to both provide the desired molecular weight and to produceeither isocyanate or hydroxyl end groups at the ends of the polyurethaneprepolymer. A polyurethane prepolymer with isocyanate functional groupson the molecular chain ends can be reacted with a monoalcohol to producea polyurethane in which the end groups are provided by the monoalcohol.A polyurethane prepolymer with alcohol functional groups on themolecular chain ends can be reacted with a monoisocyanate to produce apolyurethane in which the end groups are provided by the monoisocyanate.

In one embodiment, a polyurethane prepolymer is reacted with anothermolecule that introduces (meth)acrylate functionality. Themeth(acrylate) molecule is chosen to have functionality that iscomplementary to that of the polyurethane prepolymer that it is reactedwith. For example, for an isocyanate-terminated polyurethane prepolymer,a (meth)acrylate molecule is chosen that also contains hydroxylfunctionality (for example, HEA or HEMA). Alternatively, for ahydroxyl-terminated polyurethane prepolymer, a (meth)acrylate moleculeis chosen that also contains an isocyanate group (for example,2-isocyanatoethyl acrylate or 2-isocyanatoethyl methacrylate). Thesepolyurethane polymers with (meth)acrylate end groups are referred to aspolyurethane (meth)acrylates or urethane (meth)acrylates.

The polyisocyanate and the polyfunctional alcohol may be chosen toprovide properties desired in the resulting polyurethane (meth)acrylate,such as thermal properties (e.g., glass transition temperature), opticalproperties (e.g., transmission, haze, and clarity), solubility inselected solvents, and compatibility with other selected polymers (e.g.,poly(vinyl butyral) (PVB)).

Polyurethane (meth)acrylates may have (meth)acrylate functionality atone or more chain ends and at other sites in the polymer chain. As anonlimiting example, a (meth)acrylate diol (e.g., 2-glyceryl(meth)acrylate) may be used to make a polyurethane (meth)acrylate having(meth)acrylate groups that are at sites not near the polymer chain ends.In a preferred embodiment, a polyurethane (meth)acrylate has(meth)acrylate functionality at the chain ends.

Polyurethane (meth)acrylates may contain other functionality (e.g.,ether, ester, and/or carbonate functional groups) by selection of thestarting materials used to make them. As a nonlimiting example,poly(tetramethylene oxide) may be used to make a polyurethane(meth)acrylate that also comprises ether functional groups. Aparticularly suitable polyurethane (meth)acrylate comprises urethane,(meth)acrylate, and ether functional groups. Another particularlysuitable polyurethane (meth)acrylate comprises urethane, (meth)acrylate,and ester functional groups.

In one embodiment, the (meth)acrylate monomer includes at least one ofmonofunctional or difunctional acrylates. These (meth)acrylates canprovide increased adhesion while maintaining the optical properties ofthe adhesive formulations in which they are used. Examples of suitable(meth)acrylate monomers include, but are not limited to: cyclohexane1,4-dimethanol diacrylate; monofunctional methoxylated polyethyleneglycol 550 acrylate monomer; ethoxylated 1,6-hexanediol diacrylate;alkoxylated lauryl acrylate; 2-[[butylamino)carbonyl]oxy]ethyl acrylate;1,6 hexanediol diacrylate; tetrahydrofufuryl acrylate; phenoxyethylacrylate; ethoxylated nonylphenol acrylate; and ethoxylated phenoxyethylacrylate. Examples of suitable commercially available (meth)acrylatemonomers include, but are not limited to: CD406, CD553, CD561, CD9075,CN3100, SR238, SR285, SR339, SR504, SR9050 and SR9087, available fromSartomer Americas located in Exton, Pa., and Genomer 1122 and, availablefrom Rahn-Group located in Aurora, Ill.

A photoinitiator is used to cure the PCOCA. Typically, the initiator orinitiators are activated by exposure to light of the appropriatewavelength and intensity. Often UV light is used. Examples of suitablecommercially available photoinitators include, but are not limited to:Darocur 4265 and Irgacure 184, both available from BASF Corp. located inFlorham Park, N.J.

In one embodiment, the PCOCA optionally includes a hydroxyfunctionalmonomer with an aromatic moiety, such as the epoxy acrylate:

which constitutes the majority of the material in commercially availableSartomer CN3100, available from Sartomer Americas located in Exton, Pa.

Other materials can be added to the precursor mixture for specialpurposes, including, for example: heat stabilizers, adhesion promoters,crosslinking agents, surface modifying agents, ultraviolet lightstabilizers, antioxidants, antistatic agents, thickeners, fillers,pigments, colorants, dyes, thixotropic agents, processing aids,nanoparticles, fibers and combinations thereof.

In practice, the high performance, photocurable optically clear adhesivecan be positioned between a first substrate and a second substrate toform a laminate. The laminate includes the first substrate having atleast one major surface, the second substrate having at least one majorsurface and the PCOCA positioned adjacent the major surfaces of thefirst and second substrates. Thus, at least one of the first and secondsubstrates is optically clear and may include, for example, an opticalfilm or optically clear substrate.

The laminate including the PCOCA can be used in a display assembly. Thedisplay assembly can further include another substrate (e.g.,permanently or temporarily attached to the PCOCA), another adhesivelayer, or a combination thereof. As used herein, the term “adjacent” canbe used to refer to two layers that are in direct contact or that areseparated by one or more thin layers, such as primer or hard coating.Often, adjacent layers are in direct contact. Additionally, laminatesare provided that include the PCOCA positioned between two substrates,wherein at least one of the substrates is an optical film. Optical filmsintentionally enhance, manipulate, control, maintain, transmit, reflect,refract, absorb, retard, or otherwise alter light that impinges upon asurface of the film. Films included in the laminates include classes ofmaterial that have optical functions, such as polarizers, interferencepolarizers, reflective polarizers, diffusers, colored optical films,mirrors, louvered optical film, light control films, transparent sheets,brightness enhancement film, anti-glare, and anti-reflective films, andthe like. Films for the provided laminates can also include retarderplates such as quarter-wave and half-wave phase retardation opticalelements. Other optically clear films include anti-splinter films andelectromagnetic interference filters.

In some embodiments, the resulting laminates can be optical elements orcan be used to prepare optical elements. As used herein, the term“optical element” refers to an article that has an optical effect oroptical application. The optical elements can be used, for example, inelectronic displays, architectural applications, transportationapplications, projection applications, photonics applications, andgraphics applications. Suitable optical elements include, but are notlimited to, glazing (e.g., windows and windshields), screens ordisplays, cathode ray tubes, and reflectors.

Exemplary optically clear substrates include, but are not limited to: adisplay panel, such as liquid crystal display, an OLED display, a touchpanel or a cathode ray tube, a window or glazing, an optical componentsuch as a reflector, polarizer, diffraction grating, mirror, or coverlens, another film such as a decorative film or another optical film.

Representative examples of optically clear substrates include glass andpolymeric substrates including those that contain polycarbonates,polyesters (e.g., polyethylene terephthalates and polyethylenenaphthalates), polyurethanes, poly(meth)acrylates (e.g., polymethylmethacrylates), polyvinyl alcohols, polyolefins such as polyethylenes,polypropylenes, and cellulose triacetates. Typically, cover lenses canbe made of glass, polymethyl methacrylates, or polycarbonate.

In other embodiments, either substrate can be a release liner. Anysuitable release liner can be used. Exemplary release liners includethose prepared from paper (e.g., Kraft paper) or polymeric material(e.g., polyolefins such as polyethylene or polypropylene, ethylene vinylacetate, polyurethanes, polyesters such as polyethylene terephthalate,and the like). At least some release liners are coated with a layer of arelease agent such as a silicone-containing material or afluorocarbon-containing material. Exemplary release liners include, butare not limited to, liners commercially available from CP Film(Martinsville, Va.) under the trade designation “T-30” and “T-10” thathave a silicone release coating on polyethylene terephthalate film.

The release liner can be removed to adhere the PCOCA to anothersubstrate (i.e., removal of the release liner exposes a surface of anadhesive layer that subsequently can be bonded to another substratesurface). Often, the PCOCA is permanently bonded to this othersubstrate, although in some cases the adhesion may be limited to allowfor reworking of the display.

The high performance, photocurable optically clear adhesive of thepresent invention maintains optical clarity, bond strength, andresistance to delamination over the lifetime of the article in which itis used. As used herein, the term “optically clear” refers to a materialthat has a haze of less than about 6%, particularly less than about 4%and more particularly less than about 2%; a luminous transmission ofgreater than about 88%, particularly greater than about 89%, and moreparticularly greater than about 90%; and an optical clarity of greaterthan about 98%, particularly greater than about 99%, and moreparticularly greater than about 99.5% when cured. Typically, theclarity, haze, and transmission are measured on a construction in whichthe adhesive is held between two optical films, such as poly(ethyleneterephthalate) (PET). The measurement is then taken on the entireconstruction, including the adhesive and the substrates. Both the hazeand the luminous transmission can be determined using, for example,ASTM-D 1003-92. The optical measurements of transmission, haze, andoptical clarity can be made using, for example, a BYK Gardner haze-gardplus 4725 instrument (Geretsried, Germany). The BYK instrument uses anilluminant “C” source and measures all the light over that spectralrange to calculate a transmission value. Haze is the percentage oftransmitted light that deviates from the incident beam by more than2.5°. Optical clarity is evaluated at angles of less than 2.5°.Typically, the PCOCA is visually free of bubbles.

The high performance, photocurable optically clear adhesive of thepresent invention also has a peel adhesion of at least about 100 g/cm,particularly at least about 150 g/cm and more particularly at leastabout 200 g/cm based on ASTM 3330 when cured. If the peel adhesion ofthe PCOCA is too low, the adhesive will fail and may cause an articleincluding it to come apart (delaminate). An adhesive may fail in anumber of ways. The adhesive fails if adhesive residue remains on eitherone or both substrates positioned adjacent either side of the adhesive.

The PCOCAs of the present invention offer several advantages overpolyvinylbutyrals when used to make devices. The PCOCAs are curable, sothey can have markedly different properties before and after cure.Polyvinylbutyrals do not change properties in this manner, and thereforebehave more like hot melt adhesives. Also, because they are cured, thePCOCAs resist flow. Polyvinylbutyrals are known to flow at elevatedtemperatures, such as those an adhesive could be exposed to during themanufacture of a device. Furthermore, because they are a mixture ofcomponents, the properties of PCOCAs can be tuned to meet product needsby the choice of components and by varying the ratio of components. Thisprovides advantages in the sourcing, development, and application ofPCOCAs for new products over both the polyvinylbutyrals by themselvesand over many existing optically clear adhesives.

The laminates of the present invention have at least one of thefollowing properties: the PCOCA has optical transmissivity over a usefullifetime of the article, the PCOCA can maintain a sufficient bondstrength between layers of the article, the PCOCA can resist or avoiddelamination, and the PCOCA can resist bubbling of the adhesive layerover a useful lifetime. When used in an optical display, the laminate isoptically clear, having a haze of less than about 6%, particularly lessthan about 4% and more particularly less than about 2%; a luminoustransmission of greater than about 88%, particularly greater than about89%, and more particularly greater than about 90%; and an opticalclarity of greater than about 98%, particularly greater than about 99%,and more particularly greater than about 99.5% when cured.

Objects and advantages of this disclosure are further illustrated by thefollowing examples, but the particular materials and amounts thereofrecited in these examples, as well as other conditions and details,should not be construed to unduly limit this invention.

EXAMPLES

The present invention is more particularly described in the followingexamples that are intended as illustrations only, since numerousmodifications and variations within the scope of the present inventionwill be apparent to those skilled in the art. Unless otherwise noted,all parts, percentages, and ratios reported in the following examplesare on a weight basis.

TABLE 1 Materials Trade name or abbreviation Description Source MowitalB 14 S Poly(vinyl butyral) (PVB), Average MW 13,000 g/mol, KurarayAmerica, Inc., (B 14 S in Table 3) 14-18% poly(vinyl alcohol Houston, TXMowital B 16 H Poly(vinyl butyral) (PVB), Average MW 15,000 g/mol,Kuraray America, Inc., (B 16 H in Table 3) 18-21% poly(vinyl alcohol) inPVB Houston, TX Pioloform BL 16 H Poly(vinyl butyral),Poly(vinylformal), Average MW Kuraray America, Inc., (BL 16 H in Table 3) 23,000g/mol, 14-18% poly(vinyl alcohol Houston, TX Mowital B 20 H Poly(vinylbutyral) (PVB), Average M_(W) 23,000 g/mol, Kuraray America, Inc., (B 20H in Table 3) 18-21% poly(vinyl alcohol) in PVB Houston, TX Mowital B 30H Poly(vinyl butyral) (PVB), Average M_(W) 33,000 g/mol, KurarayAmerica, Inc., (B 30 H in Table 3) 18-21% poly(vinyl alcohol) in PVBHouston, TX Mowital B 60 H Poly(vinyl butyral) (PVB), Average M_(W)55,000 g/mol, Kuraray America, Inc., (B 60 T in Table 3) 18-2127%poly(vinyl alcohol) in PVB Houston, TX Butvar B-76 Poly(vinyl butyral)(PVB), M_(W) 90,000-120,000 g/mol, Solutia Inc., St Louis, MO (B-76 inTable 3) 11.5-13.5% poly(vinyl alcohol) in PVB Butvar B-79 Poly(vinylbutyral) (PVB), M_(W) 50,000-80,000 g/mol, Solutia Inc., St Louis, MO(B-79 in Table 3) 11.5-13.5% poly(vinyl alcohol) in PVB Butvar B-98Poly(vinyl butyral) (PVB), M_(W) 40,000-70,000 g/mol, Solutia Inc., StLouis, MO (B-98 in Table 3) 18-20% poly(vinyl alcohol) in PVB Voranol200-56 Poly(propylene oxide),~M_(W) 2,000 g/mol Dow Chemical Co.,Midland, MI PolyTHF 1000 Poly(tetramethylene oxide) (PTMO),~M_(W) 1,000g/mol BASF Corp., Florham Park, NJ Polyether PolyTHF 2000Poly(tetramethylene oxide) (PTMO),~M_(W) 2,000 g/mol BASF Corp., FlorhamPark, NJ Polyether Terethane 650 Poly(tetramethylene oxide)(PTMO),~M_(W) 650 g/mol Invista, Wichita, KS Terethane 250Poly(tetramethylene oxide) (PTMO),~M_(W) 250 g/mol Invista, Wichita, KSFomrez 55-112 Poly(neopentyl adipate) glycol, M_(W) 1,000 g/molChemtura, Middlebury, CT Capa 2100 Poly(polycaprolactone) glycolpolyester polyol, M_(W) 1,000 Perstorp, Toledo, OH g/mol C-1090Polycarbonate diol,~M_(W) 1,000 g/mol Kuraray, Houston, TX Desmodur I(IPDI) Isophorone diisocyanate Bayer Corp., Pittsburgh, PA Desmodur W4,4′-Methylene dicyclohexyl diisocyanate Bayer Corp., Pittsburgh, PA(H12MDI) HEA 2-Hydroxyethyl acrylate Sigma-Aldrich, Milwaukee, WI CN978Aromatic polyether based polyurethane diacrylate Sartomer Americas,Exton, PA CN964 Aliphatic polyester-based polyurethane diacrylateSartomer Americas, Exton, PA CN3100 Low viscosity aromatic acrylicoligomer with hydroxyl Sartomer Americas, Exton, PA functionality isbelieved to comprised mainly of

Darocur 4265 Photoinitiator BASF Corp., Florham Park, NJ DBTDLDibutyltin dilaurate Sigma-Aldrich, Milwaukee, WI MEK Methyl ethylketone Avantor Performance Materials, Center Valley, PA PETPoly(ethylene terephthalate) 5 mil Dupont Teijin Films ProfessionalPlastics, Denver, CO Melinex^(TM) 618 polyester SKC T50 tightPoly(ethylene terephthalate) silicone coated release SKC, Seoul, KRrelease liner liner-2 mil SH81 PET Skyrol SH81 2 mil primed polyesterSKC, Seoul, KR Plasma primed PET 2 mil PET, plasma treated as describedbelow 3M, St. Paul, MN SR495 Caprolactone monofunctional acrylateSartomer Americas, Exton, PA Vestanat TMDI Mixture of2,2,4-trimethy1-1,6-diisocyanatohexane and Evonik, Parsippany, NJ2,4,4-trimethy1-1,6-diisocyanatohexane HDI 1,6-diisocyanatohexane AlfaAesar, Ward Hill, MA H6XDI 1,3-bis(isocyanatomethyl)cyclohexane Aldrich,Milwaukee, WI TMXDI Tetramethyl xylylene diisocyanate Aldrich,Milwaukee, WI CD553 Monofunctional methoxylated PEG 550 acrylate monomerSartomer Americas, Exton, PA SR504 Ethoxylated nonylphenol acrylateSartomer Americas, Exton, PA SR9050 Believed to be a mixture ofmethacrylate phosphoric acid Sartomer Americas, Exton, PA ester and2-(2-Ethoxyethoxy)ethyl acrylate SR256 2-(2-Ethoxyethoxy)ethyl acrylateSartomer Americas, Exton, PA SR339 Phenoxyethyl acrylate SartomerAmericas, Exton, PA SR9087 Ethoxylated phenoxyethyl acrylate SartomerAmericas, Exton, PA SR506 Isobornyl acrylate Sartomer Americas, Exton,PA CD9075 Alkoxylated lauryl acrylate Sartomer Americas, Exton, PA SR335Lauryl acrylate Sartomer Americas, Exton, PA SR285 Tetrahydrofufurylacrylate Sartomer Americas, Exton, PA SR611 Alkoxylatedtetrahydrofufuryl acrylate Sartomer Americas, Exton, PA Genomer 1122monofunctional urethane acrylate CAS registry number Rahn, USA,Aurora,IL 63225-53-6 CD406 Cyclohexane 1,4-dimethanol diacrylateSartomer Americas, Exton, PA SR238 1,6 hexanediol diacrylate SartomerAmericas, Exton, PA CD561 Ethoxylated 1,6 hexanediol diacrylate SartomerAmericas, Exton, PA CN981 Is believed to be IPDI-ethyleneglycol-caprolactone Sartomer Americas, Exton, PA acrylated polyurethaneand hexane diol diacrylate CN991 Is believed to be H12MDI capped withSR495 Sartomer Americas, Exton, PA CN9002 Aliphatic polyurethanediacrylate (lower viscosity) Sartomer Americas, Exton, PA CN9004Aliphatic polyurethane diacrylate (higher viscosity) Sartomer Americas,Exton, PA IEA Isocyanatoethyl acrylate CBC America Corp., Commack, NY

Test Methods 180° Peel Adhesion Test

The peel adhesion test was based on ASTM D 3330. Room temperature peelswere done using an IMASS peel tester, available from IMASS, Inc.(Accord, Mass.) using a 5 kg load cell, a 4 second delay, a 20 secondtest time and a 30.48 cm/min peel rate. Three replicates were tested andthe averages are reported in grams per centimeter (g/cm).

Luminous Transmission, Clarity, and Haze

The optical measurements of transmission, haze, and optical clarity weremade using a BYK Gardner haze-gard plus 4725 instrument (Geretsried,Germany). The BYK instrument uses an illuminant “C” source and measuresall the light over that spectral range to calculate a transmissionvalue. Haze is the percentage of transmitted light that deviates fromthe incident beam by more than 2.5°. Optical clarity is evaluated atangles of less than 2.5°. Values are reported as percent transmission (%T), percent haze (% H), and percent clarity (% C) in Table 3. A samplewas considered acceptable if it had transmission of at least 88%, apercent haze of no more than 6%, and a percent clarity at least 98%after rounding.

Molecular Weight Determination

The molecular weight distribution of each polyurethane acrylate wascharacterized using conventional gel permeation chromatography (GPC).The GPC instrumentation, which was obtained from Waters Corporation(Milford, Mass., USA), included a high pressure liquid chromatographypump (Model 1515HPLC), an auto-sampler (Model 717), a UV detector (Model2487), and a refractive index detector (Model 2410). The chromatographwas equipped with two 5 micron PLgel MIXED-D columns, available fromVarian Inc. (Palo Alto, Calif., USA). Samples of polymeric solutionswere prepared by diluting polymer solution or dissolving dried polymermaterials in tetrahydrofuran (THF) at a concentration of 0.5 percent(weight/volume) and filtering the THF solution through a 0.2 micronpolytetrafluoroethylene filter that is available from VWR International(West Chester, Pa., USA). The resulting samples were injected into theGPC and eluted at a rate of 1 milliliter per minute through the columnsmaintained at 35° C. The system was calibrated with polystyrenestandards using a linear least squares fit analysis to establish acalibration curve. The weight average molecular weight (Mw) and thepolydispersity index (weight average molecular weight divided by numberaverage molecular weight) were calculated for each sample against thisstandard calibration curve.

Sample Preparation Plasma Primed PET

A roll of 125 micron thick polyethylene phthalate (PET) film was mountedon the unwind-roll of a roll-to-roll vacuum processing chamber, the filmwrapped around a drum electrode, and then secured to the take-up roll onthe opposite side of the drum electrode. The un-wind and take-uptensions were maintained at 3 pounds (13.3 N). The chamber door wasclosed and the chamber pumped down to a base pressure of about 5×10-4Torr. Hexamethyldisiloxane (HMDSO) was introduced at a flow rate of 20standard cubic centimeters per minute (sccm), and oxygen was provided ata flow rate of 500 sccm. Plasma was turned on at a power of 6000 wattsby applying radio frequency power to the drum and the drum rotationinitiated so that the film was transported at a speed of 10 feet perminute. The pressure during the exposure was around 8-10 mTorr.

Peel Test Sample Preparation

Adhesive solutions as provided in Table 3 were coated on the primedsurface of plasma primed PET using a knife coater with a 20 mil gap. Thecoated samples were dried at 70° C. for ten minutes. The samples wereremoved from the oven and an SKC T50 tight release liner was applied byhand. The samples were then cut to 1.3 cm width by 13 cm length. Floatglass panes of dimensions 6.35 cm by 17.78 cm were heated to 90° C. inan oven before lamination. The release liner was then removed from thesamples and they were laminated to the air side (non-tin) of float glassusing a hand roller. The laminated glass slides were then placed in anoven at 90° C. for 5 minutes before laminating again, using releaseliner film as an interface between the roller and the samples, toprevent contaminating the roller in case the adhesive oozed. The coatingwas then cured using a Light-Hammer 6 UV curing system (FusionUV-Systems Inc., Gaithersburg, Md.) equipped with a D bulb operatingunder nitrogen atmosphere at 100% lamp power at a line speed of 20feet/min using 4 passes.

Preparation of Polyurethane Acrylate C (16 IPDI 14 PTMO 1000 2 HEA)

A three liter three-necked round-bottomed reaction flask equipped withan overhead stirrer was charged with 99.31 g (0.8935 equivalents (eq.),111.15 eq Wt) IPDI, 480 g MEK, 386.42 g (0.7818eq, 492.27 eq Wt) PolyTHF1000 (dried overnight at 80° C. at a pressure of less than 20 mmHg) and0.25 g (500 ppm with respect to total solids) DBTDL. The flask wasplaced in an oil bath, fitted with a condenser and a temperature probe,placed under dry air, and allowed to stir. At the beginning, thereaction temperature was 28° C., at 5 min it was 29.9° C., at 13 min itwas 31.7° C., at 23 min it was 47.9° C., and at 31 min it was 53° C. Atthis time the oil bath was heated to bring the internal temperature to60° C. At 4 h and 15 min after the start of the reaction, an FTIR of areaction aliquot showed a small isocyanate peak at 2265 cm-1. At 4 h 20min after the start of the reaction, 14.23 g (0.1229 eq, 10%stoichiometric excess) HEA was added and rinsed in with 20 g MEK tobring the reaction to 50% solids. At 6 h 20 min after the start of thereaction, FTIR of a reaction aliquot showed no isocyanate peak at 2265cm-1. The reaction was then adjusted to 35% solids with 428.57 g MEK.The structures of these polyurethane acrylates are believed to be linearpolymers formed by reaction of the diols and diisocyanates to formpolyurethanes, and these linear polymers are capped on each end withhydroxyethyl acrylate (two equivalents required, but 10% stoichiometricexcess was used to ensure complete conversion). The stoichiometricamount of HEA would be 0.1229/1.1 or 0.1117 eq. The number ofequivalents of IPDI was (0.8935/0.1117)*2, or 16 equivalents, and thenumber of equivalents of the PTMO diol was (0.7818/0.1117)*2, or 14equivalents.

General Procedure for the Preparation of Polyurethane Acrylates

The procedure described above for polyurethane acrylate C was used tosynthesize the remaining polyurethane acrylates (PUA), using thestarting material weights in grams as indicated in Table 2. Thereactions were run in either a flask or a jar (with magnetic stirring)at 50% solids with 500 ppm DBTDL. All polyols were dried under vacuum(<10 torr) at 80° C. for at least two hours before use. In some cases,some reactions were diluted to 35% or 33% solids, and in some cases thereaction was left at 50% solids (indicated in Table 2) and used infurther formulations.

TABLE 2 Starting materials, percent solids of final material, andmolecular weight and polydispersity for polyurethane acrylates GramsSolids Molecular Weight Equivalent Ratios of Used in Final wt % Measuredby GPC PUA Starting Materials Formulation Solids in MEK (grams per mole)Polydispersity A 20 IPDI 15 50 17200 2.61 18 Polypropyleneoxide diol121.46 (2000 g/mol) 2 HEA 1.57 B 10 IPDI 14.35 50 15118 2.72 8 PolyTHF1000 51.64 2 HEA 3.00 C 16 IPDI 99.31 35 20482 2.65 14 PolyTHF 1000386.42 2 HEA 14.23 D 18 IPDI 21.69 50 35120 2.62 8 PolyTHF 1000 42.74 8PolyTHF 2000 85.45 2 HEA 2.83 E 16 IPDI 15.33 50 NA NA 14 PolyTHF 2000120.69 2 HEA 2 F 16 H12MDI 28.12 33.3 23455 1.39 14 PolyTHF 1000 93.77 2HEA 3.11 G 16 IPDI 25 50 18600 2.82 14 Fomrez 55-112 98.40 2 HEA 3.26 H16 IPDI 100 50 21800 2.71 14 CAPA 2100 (1000 g/mol 393.61polycaprolactonediol) 2 HEA 13.06 I 16 IPDI 12.5 50 21198 2.53 14Kuraray C-1090 49.55 2 HEA 1.63 J 16 TMDI 7.6 35 45416 1.82 14 PolyTHF1000 31.3 2 HEA 1.16 K 16 HDI 6.33 35 31327 1.73 14 PolyTHF 1000 32.53 2HEA 1.2 L 16 H6XDI 7.13 35 33455 1.64 14 PolyTHF 1000 31.75 2 HEA 1.17 M16 TMXDI 8.57 35 31270 1.72 14 PolyTHF 1000 30.36 2 HEA 1.12 N 24 IPDI9.68 50 62917 1.65 22 PolyTHF 1000 39.44 2 HEA 0.88 O 12 IPDI 10.23 5017717 1.94 10 PolyTHF 1000 37.90 2 HEA 1.87 P 14 IPDI 10.06 50 235451.89 12 PolyTHF 1000 38.36 2 HEA 1.58 Q 8 IPDI 4.88 50 30870 1.83 8H12MDI 5.76 14 PolyTHF 1000 38.01 2 HEA 1.34 R 8 IPDI 10.82 35  74492.25 6 PolyTHF 1000 36.08 2 HEA 3.11 S 6 IPDI 11.50 35  4401 2.09 4PolyTHF 1000 34.09 2 HEA 4.41 T 4 IPDI 13.16 35  2745 1.77 2 PolyTHF1000 29.27 2 HEA 7.56 U 16 IPDI 13.51 35 35491 2.13 14 PolyTHF 650 34.552 HEA 1.94 V 16 IPDI 23.50 35  7750 1.95 14 PolyTHF 250 23.12 2 HEA 3.38

Prophetic Example—Preparation of a Polyurethane Acrylate Using aHydroxyl-Terminated Prepolymer

A 500 mL three-necked round-bottomed reaction flask equipped with anoverhead stirrer is charged with 27.25 g (0.245 equivalents (eq.))isophorone diisocyanate (IPDI) and 20 g methyl ethyl ketone (MEK),placed in an oil bath, fitted with a condenser, placed under dry air,and heated to 60° C. A pressure equalizing addition funnel is chargedwith 140.1 g (0.280 eq.) of 1,000 g/mol poly(tetramethylene oxide)(PTMO, dried under vacuum (<10 torr) at 80° C. for at least two hoursbefore use) and 80 g MEK and attached to the reaction flask. To thereaction flask is added 800 microliters of a 10% solution of DBTDL inMEK. The contents of the addition funnel are then added over 30 minutesto the reaction flask, and at the end of that time, the addition funnelis rinsed with 5 g MEK, and 30 g more MEK is added directly to thereaction mixture. At 2 hours into the reaction, the reaction mixtureshows a small isocyanate peak at 2265 cm-1 by FTIR. In one portion, 4.94g (0.0350 eq.) 2-isocyanatoethyl acrylate (HEA) in 8.02 g MEK is addedto the reaction from a jar. The jar is rinsed with 5 g and then 0.5 gMEK and the rinses are added to the reaction. After about six hours,0.10 g 2-isocyanatoethyl acrylate in 5 g of MEK is added to the reactionfrom a jar. The jar is rinsed with 10 g MEK and the rinse is added tothe reaction. The mixture is allowed to react an additional 30 minutes.The product mixture is then adjusted to 50% solids by blowing dry airinto the reaction flask to evaporate some of the MEK and the productmixture is then bottled.

General Coating and Curing Procedure for Preparing Samples for OpticalTesting

Table 3 provides the composition of the solutions coated for eachexample. The abbreviations in the column labelled PVB are provided inTable 1. The polyurethane acrylate (PUA) is either described in Table 2and added at the wt % solids indicated in Table 2, or, for thecommercially available polyurethane acrylates (CN964, CN978, CN981,CN991, CN9002, and CN9004), added at 50% solids solutions in MEK, unlessotherwise noted. The photoinitiator solution is Irgacure 819 at 10 wt %in MEK. The solids weight ratios of PVB to PUA to monomer is given, andcalculated as follows: Example 1 contains 11.88 g of 25 wt % solution ofMowital B 14 S, corresponding to 2.97 g solids. It also contains 3.60 gof 33.3 wt % solution of PUA F, corresponding to 1.19 g solids. Example1 also contains 1.78 g of the CN3100 monomer. The total amount of solids(excluding Irgacure 819) was thus 2.97 g+1.19 g+1.78 g, or 5.94 g. Allsolutions were adjusted to 30 wt % solids in MEK, unless otherwisenoted, and the grams of MEK added or removed (positive or negativevalue, respectively) to reach 30 wt % solids is given. In Example 1, thesolids of Irgacure 819 was 0.1 g/g solution times 0.59 g solution=0.059g Irgacure 819. The total solids for Example 1 was 5.94 g+0.059 g, or6.00 g.

Test specimens were prepared using the adhesive solutions provided inTable 3 by coating each adhesive solution on the primed side of 2 milplasma primed PET film using a knife coater with a 25 mil gap. Thecoated PET film was air dried for about 10 minutes before being placedin a 65° C. oven for 10 minutes. The sample was then taped onto astainless steel plate pre-heated to 90° C. for about 90 sec and a secondpiece of 2 mil SSP PET film was then laminated on its primed side to thecoating. The PET-coating-PET laminate was then cured using aLight-Hammer 6 UV curing system (Fusion UV Systems Inc., Gaithersburg,Md.) equipped with a D bulb operating under nitrogen atmosphere at 100%lamp power at a line speed of 20 feet/min using 1 pass.

The percent transmission (% T), haze (% H) and clarity (% C) for eachtest specimen, and adhesion values for selected Examples and ComparativeExamples, are provided in Table 4. If a test specimen did not havedesired optical properties, adhesion was usually not tested. Thosespecimens with % T of at least 88%, % H of 6% or less, and % C of atleast 98%, and having adhesion of 100 g/cm or greater are considered tobe Examples of the invention.

TABLE 3 Adhesive Formulations Comprising PVB, Polyurethane Acrylates,and Monomers Wt % Polyurethane Grams solids Grams Polyurethane Acrylate,Grams Irgacure Ratio of in PVB PVB Acrylate grams Mono- mono- 819PVB:PUA:Mono- Example PVB solution solution Identifier solution mer mersolution mer Comparative Example 1 B 14 S 25 11.88 B 2.38 CN3100 1.780.59 50:20:30 Comparative Example 2 B 14 S 25 11.88 D 2.38 CN3100 1.780.59 50:20:30 Comparative Example 3 B 14 S 25 11.88 E 2.38 CN3100 1.780.59 50:20:30 Example 1 B 14 S 25 11.88 F 3.6 CN3100 1.78 0.59 50:20:30Comparative Example 4 B 14 S 25 11.88 G 2.38 CN3100 1.78 0.59 50:20:30Example 2 B 14 S 25 11.88 H 2.38 CN3100 1.78 0.59 50:20:30 ComparativeExample 5 B 14 S 25 11.88 I 2.38 CN3100 1.78 0.59 50:20:30 ComparativeExample 6 B 14 S 25 11.88 J 3.39 CN3100 1.78 0.59 50:20:30 Example 3 B14 S 25 11.88 K 3.39 CN3100 1.78 0.59 50:20:30 Comparative Example 7 B14 S 25 11.88 L 3.39 CN3100 1.78 0.59 50:20:30 Comparative Example 8 B14 S 25 11.88 M 3.39 CN3100 1.78 0.59 50:20:30 Example 4 B 14 S 25 11.88C 3.39 CN3100 1.78 0.59 50:20:30 Example 5 B 14 S 30 9.90 C 6.79 CN31000.59 0.59 50:40:10 Example 6 B 14 S 30 9.90 C 6.79 CN3100 0.59 0.5950:40:10 Example 7 B 14 S 30 9.90 C 1.7 CN3100 2.38 0.59 50:10:40Example 8 B 14 S 30 7.92 C 5.09 CN3100 1.78 0.59 40:30:30 Example 9 B 14S 30 5.94 C 1.7 CN3100 3.56 0.59 30:10:60 Example 10 B 14 S 30 5.94 C5.94 CN3100 2.08 0.59 30:35:35 Example 11 B 14 S 30 5.94 C 10.18 CN31000.59 0.59 30:60:10 Comparative Example 9 B 14 S 25 11.88 N 2.35 CN31001.78 0.59 50:20:30 Comparative Example 10 B 14 S 25 11.88 O 2.35 CN31001.78 0.59 50:20:30 Example 12 B 14 S 25 11.88 P 2.35 CN3100 1.78 0.5950:20:30 Comparative Example 11 B 14 S 25 11.88 Q 2.35 CN3100 1.78 0.5950:20:30 Comparative Example 12 B 14 S 30 9.90 R 2.38 CN3100 1.78 0.5953.2:14.9:31.9 Comparative Example 13 B 14 S 30 9.90 S 2.38 CN3100 1.780.59 53.2:14.9:31.9 Comparative Example 14 B 14 S 30 9.90 T 2.38 CN31001.78 0.59 53.2:14.9:31.9 Example 13 B 14 S 30 9.90 U 2.38 CN3100 1.780.59 53.2:14.9:31.9 Example 14 B 14 S 30 9.90 V 2.38 CN3100 1.78 0.5953.2:14.9:31.9 Comparative Example 15 B 14 S 30 9.90 CN964 2.38 CN31001.78 0.59 50:20:30 Comparative Example 16 B 14 S 30 9.90 CN978 2.38CN3100 1.78 0.59 50:20:30 Comparative Example 17 B 14 S 30 9.90 CN9812.38 CN3100 1.78 0.59 50:20:30 Comparative Example 18 B 14 S 30 9.90CN991 1.19 CN3100 1.78 0.59 50:20:30 (100% solids) Comparative Example19 B 14 S 30 9.90 CN9002 2.38 CN3100 1.78 0.59 50:20:30 ComparativeExample 20 B 14 S 30 9.90 CN9004 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 21 B 16 H 30 9.90 H 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 22 B 16 H 30 9.90 L 3.39 CN3100 1.78 0.59 50:20:30Comparative Example 23 B 16 H 30 9.90 C 6.79 CN3100 0.59 0.59 50:40:10Comparative Example 24 B 16 H 25 11.88 C 3.39 CN3100 1.78 0.59 50:20:30Comparative Example 25 B 16 H 30 9.90 C 1.7 CN3100 2.38 0.59 50:10:40Comparative Example 26 B 16 H 30 7.92 C 5.09 CN3100 1.78 0.59 40:30:30Comparative Example 27 B 20 H 25 11.88 B 3.6 CN3100 1.78 0.59 50:20:30Comparative Example 28 B 20 H 25 11.88 D 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 29 B 20 H 25 11.88 E 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 30 B 20 H 25 11.88 F 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 31 B 20 H 25 11.88 G 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 32 B 20 H 25 11.88 H 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 33 B 20 H 25 11.88 I 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 34 B 20 H 25 11.88 J 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 35 B 20 H 25 11.88 K 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 36 B 20 H 25 11.88 L 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 37 B 20 H 25 11.88 F 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 38 B 20 H 30 9.90 C 6.79 CN3100 0.59 0.59 50:40:10Comparative Example 39 B 20 H 30 9.90 C 3.39 CN3100 1.78 0.59 50:20:30Comparative Example 40 B 20 H 30 9.90 C 1.7 CN3100 2.38 0.59 50:10:40Comparative Example 41 B 20 H 30 7.92 C 5.09 CN3100 1.78 0.59 40:30:30Comparative Example 42 B 20 H 25 11.88 N 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 43 B 20 H 25 11.88 O 2.38 CN3100 1.78 0.59 50:20:30Comparative Example 44 B 20 H 25 11.88 P 2.38 CN3100 1.78 0.59 50:20:30Example 15 B 20 H 25 11.88 Q 2.38 CN3100 1.78 0.59 50:20:30 ComparativeExample 45 B 30 H 25 11.88 C 3.39 CN3100 1.78 0.59 50:20:30 ComparativeExample 46 BL 16 H 25 11.88 H 2.38 CN3100 1.78 0.59 50:20:30 ComparativeExample 47 BL 16 H 25 11.88 L 3.39 CN3100 1.78 0.59 50:20:30 ComparativeExample 48 BL 16 H 25 11.88 C 1.7 CN3100 2.38 0.59 50:10:40 ComparativeExample 49 B-76 25 11.88 C 3.39 CN3100 1.78 0.59 50:20:30 ComparativeExample 50 B 30 H 20 10 C 1.6 CN3100 1.2 0.2 50:20:30 (50% solids)Comparative Example 51 B 60 H 15 13.3 C 1.6 CN3100 1.2 0.2 50:20:30 (50%solids) Comparative Example 52 B-79 20 10 C 1.6 CN3100 1.2 0.2 50:20:30(50% solids) Comparative Example 53 B-98 20 10 C 1.6 CN3100 1.2 0.250:20:30 (50% solids) Example 16 B 14 S 25 11.88 C 3.39 CD553 1.78 0.5950:20:30 Comparative Example 54 B 16 H 30 9.9 C 6.79 CD553 0.59 0.5950:40:10 Comparative Example 55 B 16 H 30 9.9 C 3.39 CD553 1.78 0.5950:20:30 Comparative Example 56 B 16 H 30 9.9 C 1.7 CD553 2.38 0.5950:10:40 Comparative Example 57 B 16 H 30 7.92 C 5.09 CD553 1.78 0.5940:30:30 Comparative Example 58 B 20 H 30 9.9 C 6.79 CD553 0.59 0.5950:40:10 Comparative Example 59 B 20 H 30 9.9 C 3.39 CD553 1.78 0.5950:20:30 Comparative Example 60 B 20 H 30 9.9 C 1.7 CD553 2.38 0.5950:10:40 Comparative Example 61 B 20 H 30 7.92 C 5.09 CD553 1.78 0.5940:30:30 Example 17 B 14 S 25 11.88 C 3.88 SR504 1.78 0.59 50:20:30Comparative Example 62 B 16 H 30 9.9 C 6.79 SR504 0.59 0.59 50:40:10Comparative Example 63 B 16 H 30 9.9 C 3.39 SR504 1.78 0.59 50:20:30Example 18 B 16 H 30 9.9 C 1.7 SR504 2.38 0.59 50:10:40 ComparativeExample 64 B 16 H 30 7.92 C 5.09 SR504 1.78 0.59 40:30:30 ComparativeExample 65 B 20 H 30 9.9 C 6.79 SR504 0.59 0.59 50:40:10 Example 19 B 20H 30 9.9 C 3.39 SR504 1.78 0.59 50:20:30 Example 20 B 20 H 30 9.9 C 1.7SR504 2.38 0.59 50:10:40 Comparative Example 66 B 20 H 30 7.92 C 5.09SR504 1.78 0.59 40:30:30 Comparative Example 67 BL 16 H 25 11.88 C 3.39SR504 1.78 0.59 50:20:30 Example 21 B 14 S 25 11.88 B 2.38 SR9050 1.780.59 50:20:30 Example 22 B 14 S 25 11.88 D 2.38 SR9050 1.78 0.5950:20:30 Comparative Example 68 B 14 S 25 11.88 G 2.38 SR9050 1.78 0.5950:20:30 Example 23 B 14 S 25 11.88 H 2.38 SR9050 1.78 0.59 50:20:30Example 24 B 14 S 30 13.86 C 2.55 SR9050 0.89 0.59 70:15:15 Example 25 B14 S 30 11.88 C 3.39 SR9050 1.19 0.59 60:20:20 Example 26 B 14 S 2511.88 C 3.39 SR9050 1.78 0.59 50:20:30 Example 27 B 14 S 30 5.94 C 5.94SR9050 2.08 0.59 30:35:35 Example 28 B 14 S 25 11.88 N 2.38 SR9050 1.780.59 50:20:30 Example 29 B 14 S 25 11.88 Q 2.38 SR9050 1.78 0.5950:20:30 Example 30 B 14 S 30 9.90 R 2.38 SR9050 1.78 0.5953.2:14.9:31.9 Example 31 B 14 S 30 9.90 S 2.38 SR9050 1.78 0.5953.2:14.9:31.9 Example 32 B 14 S 30 9.90 T 2.38 SR9050 1.78 0.5953.2:14.9:31.9 Example 33 B 14 S 30 9.90 U 2.38 SR9050 1.78 0.5953.2:14.9:31.9 Comparative Example 69 B 14 S 30 9.90 V 2.38 SR9050 1.780.59 53.2:14.9:31.9 Example 34 B 14 S 30 9.90 A 2.38 SR9050 1.78 0.5950:20:30 Example 35 B 16 H 25 11.88 D 2.38 SR9050 1.78 0.59 50:20:30Comparative Example 70 B 16 H 25 11.88 E 2.38 SR9050 1.78 0.59 50:20:30Example 36 B 16 H 25 11.88 F 3.6 SR9050 1.78 0.59 50:20:30 ComparativeExample 71 B 16 H 25 11.88 G 2.38 SR9050 1.78 0.59 50:20:30 Example 37 B16 H 25 11.88 H 2.38 SR9050 1.78 0.59 50:20:30 Comparative Example 72 B16 H 25 11.88 I 2.38 SR9050 1.78 0.59 50:20:30 Example 38 B 16 H 2511.88 J 3.39 SR9050 1.78 0.59 50:20:30 Example 39 B 16 H 25 11.88 K 3.39SR9050 1.78 0.59 50:20:30 Example 40 B 16 H 25 11.88 L 3.39 SR9050 1.780.59 50:20:30 Example 41 B 16 H 25 11.88 M 3.39 SR9050 1.78 0.5950:20:30 Comparative Example 73 B 16 H 30 13.86 C 2.55 SR9050 0.89 0.5970:15:15 Example 42 B 16 H 30 11.88 C 3.39 SR9050 1.19 0.59 60:20:20Comparative Example 74 B 16 H 30 9.90 C 6.79 SR9050 0.59 0.59 50:40:10Example 43 B 16 H 30 9.90 C 3.39 SR9050 1.78 0.59 50:20:30 Example 44 B16 H 30 10.00 C 1.70 SR9050 2.4 0.59 50:10:40 Example 45 B 16 H 30 7.92C 5.09 SR9050 1.78 0.59 40:30:30 Comparative Example 75 B 16 H 30 5.94 C10.18 SR9050 0.59 0.59 30:60:10 Example 46 B 16 H 30 5.94 C 5.94 SR90502.08 0.59 30:35:35 Example 47 B 16 H 30 5.94 C 1.70 SR9050 3.56 0.5930:10:60 Example 48 B 16 H 25 11.88 Q 3.39 SR9050 1.78 0.59 50:20:30Example 49 B 20 H 25 11.88 B 3.60 SR9050 1.78 0.59 50:20:30 Example 50 B20 H 25 11.88 D 2.38 SR9050 1.78 0.59 50:20:30 Comparative Example 76 B20 H 25 11.88 E 2.38 SR9050 1.78 0.59 50:20:30 Example 51 B 20 H 2511.88 F 3.6 SR9050 1.78 0.59 50:20:30 Comparative Example 77 B 20 H 2511.88 G 2.38 SR9050 1.78 0.59 50:20:30 Example 52 B 20 H 25 11.88 H 2.38SR9050 1.78 0.59 50:20:30 Comparative Example 78 B 20 H 25 11.88 I 2.38SR9050 1.78 0.59 50:20:30 Example 53 B 20 H 25 11.88 J 3.39 SR9050 1.780.59 50:20:30 Example 54 B 20 H 25 11.88 K 3.39 SR9050 1.78 0.5950:20:30 Example 55 B 20 H 25 11.88 L 3.39 SR9050 1.78 0.59 50:20:30Comparative Example 79 B 20 H 25 11.88 M 3.39 SR9050 1.78 0.59 50:20:30Comparative Example 80 B 20 H 30 13.86 C 2.55 SR9050 0.89 0.59 70:15:15Comparative Example 81 B 20 H 30 11.88 C 3.39 SR9050 1.19 0.59 60:20:20Comparative Example 82 B 20 H 30 9.90 C 6.79 SR9050 0.59 0.59 50:40:10Example 56 B 20 H 25 11.88 C 3.39 SR9050 1.78 0.59 50:20:30 Example 57 B20 H 30 9.9 C 1.7 SR9050 2.38 0.59 50:10:40 Example 58 B 20 H 30 7.92 C5.09 SR9050 1.78 0.59 40:30:30 Comparative Example 83 B 20 H 30 5.94 C10.18 SR9050 0.59 0.59 30:60:10 Comparative Example 84 B 20 H 30 5.94 C5.94 SR9050 2.08 0.59 30:35:35 Example 59 B 20 H 30 5.94 C 1.70 SR90503.56 0.59 30:10:60 Example 60 B 20 H 25 11.88 N 2.38 SR9050 1.78 0.5950:20:30 Comparative Example 85 BL 16 H 25 11.88 C 3.39 SR9050 1.78 0.5950:20:30 Example 61 B 14 S 30 9.90 C 3.39 CD406 (40 4.46 0.59 50:20:30wt % in MEK) Example 62 B 14 S 30 9.90 C 3.39 CD561 1.78 0.59 50:20:30Comparative Example 86 B 14 S 30 9.90 C 3.39 CD9075 1.78 0.59 50:20:30Example 63 B 14 S 30 9.90 C 3.39 Genorad 1122 1.78 0.59 50:20:30Comparative Example 87 B 14 S 30 9.90 C 3.39 SR256 1.78 0.59 50:20:30Comparative Example 88 B 14 S 30 9.90 C 3.39 SR285 1.78 0.59 50:20:30Comparative Example 89 B 14 S 30 9.90 C 3.39 SR335 1.78 0.59 50:20:30Comparative Example 90 B 14 S 30 9.90 C 3.39 SR506 1.78 0.59 50:20:30Comparative Example 91 B 14 S 30 9.90 C 3.39 SR611 1.78 0.59 50:20:30Example 64 B 14 S 30 9.90 C 3.39 SR238 1.78 0.59 50:20:30 Example 65 B14 S 30 9.90 C 3.39 SR339 1.78 0.59 50:20:30 Comparative Example 92 B 14S 30 9.90 C 3.39 SR602 1.78 0.59 50:20:30 Example 66 B 14 S 30 9.90 C3.39 SR9087 1.78 0.59 50:20:30 Comparative Example 93 B 16 H 30 9.9 C3.39 CD406 (40 4.46 0.59 50:20:30 wt % in MEK) Comparative Example 94 B16 H 30 9.9 C 3.39 CD561 1.78 0.59 50:20:30 Example 67 B 16 H 30 9.9 C3.39 Genorad 2250 1.78 0.59 50:20:30 Comparative Example 95 B 16 H 309.9 C 3.39 SR238 1.78 0.59 50:20:30 Example 68 B 16 H 30 9.9 C 3.39SR339 1.78 0.59 50:20:30 Comparative Example 96 B 16 H 30 10.09 C 3.46SR602 1.82 0.61 50:20:30 Example 69 B 16 H 30 9.9 C 3.39 SR9087 1.780.59 50:20:30 Comparative Example 98 B 20 H 30 9.9 C 3.39 CD406 (40 4.460.59 50:20:30 wt % in MEK) Example 70 B 20 H 30 9.9 C 3.39 CD561 1.780.59 50:20:30 Example 71 B 20 H 30 9.9 C 3.39 Genorad 2250 1.78 0.5950:20:30 Example 72 B 20 H 30 9.9 C 3.39 SR238 1.78 0.59 50:20:30Example 73 B 20 H 30 9.9 C 3.39 SR339 1.78 0.59 50:20:30 ComparativeExample 99 B 20 H 30 9.9 C 3.39 SR602 1.78 0.59 50:20:30 Example 74 B 20H 30 9.9 C 3.39 SR9087 1.78 0.59 50:20:30

TABLE 4 Optical Properties and Peel Adhesion Example T (%) H (%) C (%)Adhesion (g/cm) Comparative Example 1 89.5 1.3 99.7 56 ComparativeExample 2 89.1 4.23 88.5 21 Comparative Example 3 89.4 11.6 78.0 No dataExample 1 89.7 1.02 100.0 164 Comparative Example 4 89.7 1.78 98.7 23Example 2 88.4 2.63 100.0 500 Comparative Example 5 84.8 2.46 94.8 174Comparative Example 6 87.5 25.5 99.4 No data Example 3 88.6 0.69 100.0162 Comparative Example 7 89.3 0.73 95.1 413 Comparative Example 8 88.745 99.6 No data Example 4 88.1 0.8 99.4 491 Example 5 89 4.85 99.2 864Example 6 89.2 5.26 98.3 577 Example 7 89.2 0.99 99.7 251 Example 8 89.21.98 100.0 156 Example 9 89.5 1.88 99.7 169 Example 10 88.8 0.72 100.0307 Example 11 89.4 0.37 100.0 111 Comparative Example 9 89 4.53 97.7 85Comparative Example 10 89.4 1.35 99.3 60 Example 12 89.6 1.45 100.0 110Comparative Example 11 89.5 1.55 99.7 50 Comparative Example 12 89.60.65 99.6 78 Comparative Example 13 89.7 0.85 99.7 51 ComparativeExample 14 89.6 0.92 98.9 70 Example 13 89.9 0.87 99.7 993 Example 14 900.53 99.8 100 Comparative Example 15 89.8 1.19 100.0 81 ComparativeExample 16 89.8 0.52 97.8 44 Comparative Example 17 89.7 0.47 99.7 50Comparative Example 18 89.8 0.51 99.8 24 Comparative Example 19 89.30.84 99.7 19 Comparative Example 20 89.4 19.6 98.3 No data ComparativeExample 21 88.7 1.39 99.7 16 Comparative Example 22 88.1 2.9 100.0 25Comparative Example 23 88.3 13.6 74.9 No data Comparative Example 2489.3 1 99.8 56 Comparative Example 25 89.5 0.79 100.0 23 ComparativeExample 26 89.2 1.58 95.6 22 Comparative Example 27 87.8 3.36 100.0 10Comparative Example 28 89.1 52.4 80.0 13 Comparative Example 29 89.5 3171.9 No data Comparative Example 30 88.4 4.52 96.7 No data ComparativeExample 31 89.8 3.58 96.5 50 Comparative Example 32 89.9 1.87 100.0 6Comparative Example 33 89.6 3.72 94.8 No data Comparative Example 3487.7 45.8 96.0 No data Comparative Example 35 84.5 6.22 100.0 No dataComparative Example 36 88.6 2.32 100.0 12 Comparative Example 37 88.81.31 99.3 17 Comparative Example 38 88.9 8.05 83.3 No data ComparativeExample 39 88.9 1.19 99.8 11 Comparative Example 40 89.1 0.58 100.0 28Comparative Example 41 89.2 2.01 95.5 40 Comparative Example 42 89.230.8 88.8 No data Comparative Example 43 87.7 4.92 100.0 17 ComparativeExample 44 89.5 26.5 99.8 No data Example 15 88.5 2.8 99.7 696Comparative Example 45 88.7 1.59 100.0 8 Comparative Example 46 88.62.48 99.8 9 Comparative Example 47 89.3 6.51 100.0 No data ComparativeExample 48 89.2 3.66 99.7 70 Comparative Example 49 87.9 3.45 100.0 41Comparative Example 50 91.1 10.3 64.9 No data Comparative Example 5190.9 20.9 48.3 No data Comparative Example 52 91.3 0.12 93.9 No dataComparative Example 53 89.6 11.1 58.7 No data Example 16 89 2.05 99.81600 Comparative Example 54 89.2 11.9 72.7 No data Comparative Example55 89.2 7.05 98.9 No data Comparative Example 56 89.6 9.54 100 No dataComparative Example 57 88.9 5.52 93.8 No data Comparative Example 5887.8 19.3 76.1 No data Comparative Example 59 88.5 14.8 97.2 No dataComparative Example 60 89 6.11 99.8 59 Comparative Example 61 88.8 8.8192.6 No data Example 17 89.5 0.83 97.7 2500 Comparative Example 62 89.112.5 77.6 No data Comparative Example 63 89.7 2.07 95.5 711 Example 1889.2 1.04 99.8 870 Comparative Example 64 89.3 3.64 86.3 64 ComparativeExample 65 88.8 12.8 86 No data Example 19 89.2 3.02 98.3 910 Example 2089.3 0.74 99.8 1500 Comparative Example 66 89.4 2.99 91.1 No dataComparative Example 67 89.2 5.63 86.5 No data Example 21 88.2 0.5 99.71073 Example 22 88.2 1.22 99.7 1148 Comparative Example 68 88.7 4.4999.7 74 Example 23 88.7 0.7 99.5 165 Example 24 88.7 1.34 99.2 292Example 25 88.7 0.46 100 1672 Example 26 89.5 0.54 100 2500 Example 2789.1 1.34 99.6 146 Example 28 88.7 0.61 100 1398 Example 29 88.8 0.3899.8 1355 Example 30 89.7 0.89 99.5 971 Example 31 89.9 0.68 99.7 936Example 32 89.7 0.81 99.3 497 Example 33 89.8 1.88 99.3 927 ComparativeExample 69 89.4 1.74 94.4 No data Example 34 89.1 3.06 99.5 224 Example35 88.2 0.76 99.8 1507 Comparative Example 70 88.5 16.6 98 No dataExample 36 88.6 0.5 100 628 Comparative Example 71 88.4 11.87 99 No dataExample 37 88.7 1 99.8 121 Comparative Example 72 88.7 4.78 90 No dataExample 38 88.4 1.1 99.6 1326 Example 39 88.8 0.56 99.8 1010 Example 4088.7 0.91 99.7 585 Example 41 88.6 1.14 99.3 168 Comparative Example 7388.8 0.42 99.4 38 Example 42 88.6 1 99.2 327 Comparative Example 74 89.27.61 93.3 No data Example 43 88.8 0.8 99.8 1921 Example 44 89.4 0.8599.8 1500 Example 45 89.1 0.92 100 1840 Comparative Example 75 88.7 3.9399.6 50 Example 46 88.4 0.89 100 249 Example 47 88.7 0.37 100 246Example 48 88.7 0.48 99.6 1227 Example 49 88.7 1.56 99.4 731 Example 5088 1.13 99.1 1346 Comparative Example 76 89.3 21.3 98.1 782 Example 5188.8 1.1 99.6 593 Comparative Example 77 87.7 9.87 99.5 No data Example52 88.6 1.17 99.1 205 Comparative Example 78 88.5 6.48 95.2 No dataExample 53 88.9 0.77 99.7 1395 Example 54 88.2 0.51 99.8 659 Example 5588.8 0.79 99.7 316 Comparative Example 79 88.8 0.76 99 58 ComparativeExample 80 88.4 0.73 98.9 33 Comparative Example 81 88.8 0.46 99.8 13Comparative Example 82 89.2 6.85 91.8 No data Example 56 88.6 1.02 99.62500 Example 57 89.2 0.53 99.7 1809 Example 58 89.2 0.58 99.8 1554Comparative Example 83 88.8 2.62 99.7 30 Comparative Example 84 88.40.42 100 13 Example 59 88.5 0.36 100 126 Example 60 88.6 0.62 99.6 365Comparative Example 85 88.6 20.5 96.3 No data Example 61 89.1 1.04 99.8500 Example 62 89.7 0.90 100 1500 Comparative Example 86 89.1 0.8 94.2974 Example 63 89.5 0.76 99.7 1335 Comparative Example 87 88.8 6.47 86.8No data Comparative Example 88 88.1 4.04 80.6 1196 Comparative Example89 89.2 2.42 97 495 Comparative Example 90 88.0 2.55 94.3 2500Comparative Example 91 89.1 1.34 93.2 1574 Example 64 89.5 0.59 98 2000Example 65 89.1 0.86 98.4 2400 Comparative Example 92 85.2 17.60 99 Nodata Example 66 89.5 0.65 97.5 1220 Comparative Example 93 89.4 1.0799.7 15 Comparative Example 94 89.6 4.43 97.2 380 Example 67 89.6 0.7499.7 1713 Comparative Example 95 89.7 1.04 97 1000 Example 68 89.3 1.2899.4 1682 Comparative Example 96 86.3 35.00 96.8 No data Example 69 89.61.08 99.1 1010 Comparative Example 98 89.6 0.76 99.6 12 Example 70 89.54.10 99.2 367 Example 71 89.5 0.78 99.7 1460 Example 72 89.7 1.21 97.8250 Example 73 89.2 1.91 99.5 1708 Comparative Example 99 88.2 51.50 99No data Example 74 89.6 1.16 99.6 1266

Although the present invention has been described with reference topreferred embodiments, workers skilled in the art will recognize thatchanges may be made in form and detail without departing from the spiritand scope of the invention.

1. An optically clear, curable adhesive comprising: a polyvinylbutyralhaving a dynamic viscosity of between about 9 and about 30 mPA·s andhaving a polyvinyl alcohol weight percent of between about 14% and about21%; a polyurethane (meth)acrylate comprising the reaction product of: adiol; at least one diisocyanate; and a hydroxyfunctional (meth)acrylateor an isocyanatofunctional (meth)acrylate; a (meth)acrylate monomer; anda photoinitiator; wherein when the optically clear, curable adhesive isplaced between two transparent substrates and made into a laminate, thelaminate has a haze of less than about 6%, a transmission of greaterthan about 88% and optical clarity of greater than about 98% when cured,and wherein the optically clear, curable adhesive has a peel adhesion ofat least about 100 g/cm based on ASTM 3330 when cured.
 2. The opticallyclear, curable adhesive of claim 1, wherein the diol is selected fromone of a poly(tetramethylene oxide) diol having a number averagemolecular weight of about 2000 g/mol or less, a poly(propylene oxide)diol having a number average molecular weight of about 2000 g/mol orless, and a polycaprolactone diol having a number average molecularweight of about 2000 g/mol or less.
 3. The optically clear, curableadhesive of claim 1, wherein the diisocyanate is an aliphaticdiisocyanate.
 4. (canceled)
 5. The optically clear, curable adhesive ofclaim 1, further comprising a hydroxyfunctional monomer with an aromaticmoiety.
 6. The optically clear, curable adhesive of claim 1, wherein thepolyvinylbutyral has a weight average molecular weight between about10,000 g/mol and about 25,000 g/mol.
 7. The optically clear, curableadhesive of claim 1, wherein the polyurethane (meth)acrylate has aweight average molecular weight between about 2,745 g/mol and about63,000 g/mol.
 8. The optically clear, curable adhesive of claim 1,wherein the polyvinylbutyral has a polyvinyl acetate weight percent ofbetween about 1% and about 8%.
 9. The optically clear, curable adhesiveof claim 1, wherein the optically clear, curable adhesive comprisesbetween about 30% and about 70% by weight polyvinylbutyral.
 10. Theoptically clear, curable adhesive of claim 1, wherein the opticallyclear, curable adhesive comprises between about 10% and about 60% byweight polyurethane (meth)acrylate.
 11. The optically clear, curableadhesive of claim 1, wherein the optically clear, curable adhesivecomprises between about 10% and about 60% by weight (meth)acrylatemonomer.
 12. The optically clear, curable adhesive of claim 1, whereinthe (meth)acrylate monomer comprises at least one of monofunctional ordifunctional acrylates.
 13. An optically clear laminate comprising: afirst substrate; a second substrate; and an optically clear, curableadhesive positioned between the first substrate and the secondsubstrate, the optically clear, curable adhesive comprising: apolyvinylbutyral having a dynamic viscosity of between about 9 and about30 mPA·s and having a polyvinyl alcohol weight percent of between about14% and about 21%; a polyurethane (meth)acrylate comprising the reactionproduct of: a diol; at least one diisocyanate; and a hydroxyfunctional(meth)acrylate or an isocyanatofunctional (meth)acrylate; a(meth)acrylate monomer; and a photoinitiator; wherein when the opticallyclear, curable adhesive is placed between two transparent substrates andmade into a laminate, the laminate has a haze of less than about 6%, atransmission of greater than about 88% and optical clarity of greaterthan about 98% when cured, and wherein the optically clear, curableadhesive has a peel adhesion of at least about 100 g/cm based on ASTM3330 when cured.
 14. The optically clear laminate of claim 13, whereinthe diol is selected from one of a poly(tetramethylene oxide) diolhaving a number average molecular weight of about 2000 g/mol or less, apoly(propylene oxicde) diol having a number average molecular weight ofabout 2000 g/mol or less and a polycaprolactone diol having a numberaverage molecular weight of about 2000 g/mol or less.
 15. The opticallyclear laminate of claim 13, wherein the diisocyanate is an aliphaticdiisocyanate.
 16. The optically clear laminate of claim 13, wherein thepolyvinylbutyral has a weight average molecular weight between about10,000 g/mol and about 25,000 g/mol.
 17. The optically clear laminate ofclaim 13, wherein the polyurethane (meth)acrylate has a weight averagemolecular weight between about 2,745 g/mol and about 63,000 g/mol. 18.The optically clear laminate of claim 13, wherein the polyvinylbutyralhas a polyvinyl acetate weight percent of between about 1% and about 8%.19. The optically clear laminate of claim 13, wherein the opticallyclear, curable adhesive comprises between about 30% and about 70% byweight polyvinylbutyral.
 20. The optically clear laminate of claim 13,wherein the optically clear, curable adhesive comprises between about10% and about 60% by weight polyurethane (meth)acrylate.
 21. Theoptically clear laminate of claim 13, wherein the optically clear,curable adhesive comprises between about 10% and about 60% by weight(meth)acrylate monomer.